CN103030784A - Sulfur-containing hyperbranched epoxy resin and preparation method thereof - Google Patents
Sulfur-containing hyperbranched epoxy resin and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of epoxy resins and preparation method thereof and in particular discloses a sulfur-containing hyperbranched epoxy resin and a preparation method thereof. The preparation method comprises the following steps: stirring and reacting a trithiol compound and a diolefin compound at the temperature of 10 DEG C below zero and 20 DEG C for 2-5 hours and preparing an acrylate monomer with polyfunctionality; stirring and reacting the monomer and bithiol secondary amine at the temperature of 20-80 DEG C for 5-10 hours and obtaining a first generation mercapto-terminated hyperbranched polymer NP1-HSH; stirring and reacting the NP1-HSH and methacrylic acid glycidyl ester at the temperature of 10 DEG C below zero and 20 DEG C for 2-5 hours and obtaining a first generation sulfur-containing hyperbranched epoxy resin; and sequentially carrying out the previous three reactions on NP1-HSH to prepare a second-fourth generation sulfur-containing hyperbranched epoxy resin with the molecular weight of about 2,000-30,000 g/mol. The method is simple in process and low in reaction temperature, the obtained product can reduce the curing temperature and is expected to be applied to the fields of reinforcing and toughening of epoxy resins, solvent-free coatings and the like.
Description
Technical field
The present invention relates to sulfur-bearing hyperbranched epoxy resin and preparation method thereof technical field, be specifically related to a kind of sulfur-bearing hyperbranched epoxy resin and preparation method thereof, the method is a kind of method for preparing the sulfur-bearing hyperbranched epoxy resin by mercaptan-alkene hydrocarbon click-reaction technique to high-efficiency.
Background technology
The study on the synthesis of sulfur-bearing hyperbranched epoxy resin originated from 1993.PCT International Application No. WO 9317060 has disclosed take dimethylol propionic acid as raw material, TriMethylolPropane(TMP) and epichlorohydrin reaction can synthesize the higher aliphatics sulfur-bearing hyperbranched epoxy resin of viscosity.The viscosity of present inventor (Zhang Daohong) sulfur-bearing hyperbranched epoxy resin of preparation take trimellitic acid 1,2-anhydride, glycol ether, ethylene glycol, glycol ether, epoxy chloropropane as main raw material is low, but not high (the European PolymerJournal of thermotolerance, 2006,42 (3): 711-714).The present inventor has also invented the high nitrogen heterocyclic sulfur-bearing hyperbranched epoxy resin of heat resisting temperature and the sulfur-bearing hyperbranched epoxy resin (ZL200910029024.9, ZL200910029026.8, ZL200910062871.5, ZL201010224451.5) of silicon skeleton.The preparation technology of these sulfur-bearing hyperbranched epoxy resins need to add a large amount of organic solvents usually, large Alternative all needed water-washing step after reaction was finished, environment there is certain pollution, the efficient of the technology of preparing of the sulfur-bearing hyperbranched epoxy resin of reporting in addition (esterification, addition reaction of silicon with hydrogen, graft reaction, GROUP TRANSFER POLYMERIZATION) is on the low side, productive rate is not high, the long reaction time energy consumption is large, and temperature is high during curing, the time is long.Therefore the technology of preparing of the sulfur-bearing hyperbranched epoxy resin that development technology is simple, the reaction times is short, set time is short, solidification value is low is to solve the at present fundamental way of the problem of this field existence.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of new sulfur-bearing hyperbranched epoxy resin is provided, its structural formula is Gn,
In the formula, A, B, C, D represent respectively-SH ,-NH-, CH
2=C (CH
3) COO-and CH
2=CHCOO-; Respectively from the functional group among compound A-13, Compound C D, the compd B A2.
In the formula, compound GMA is glycidyl methacrylate.
Wherein compound A-13 is trimethylolpropane tris mercaptoacetate (TMP-TEA), trimethylolpropane tris mercaptopropionic acid ester (TMP-TPA), tris(2-hydroxy ethyl)isocyanurate tri-thiol acetic ester (THEIC-TEA) or tris(2-hydroxy ethyl)isocyanurate tri-thiol propionic ester (THEIC-TPA), and these compounds can obtain by corresponding trivalent alcohol and Thiovanic acid or thiohydracrylic acid esterification reaction.
Another object of the present invention has been to provide a kind of preparation method of sulfur-bearing hyperbranched epoxy resin of aforementioned structure, and the reaction formula of its whole process is as follows:
For the reaction formula to above-mentioned whole process is further elaborated, this preparation method's concrete steps are as follows:
(a) tri-thiol compound A-13 and diolefin compound CD are prepared the acrylate monomer D3 of polyfunctionality at-10-20 ℃ stirring reaction 2-5h;
Described tri-thiol compound A-13 is trimethylolpropane tris mercaptoacetate (TMP-TEA), trimethylolpropane tris mercaptopropionic acid ester (TMP-TPA), tris(2-hydroxy ethyl)isocyanurate tri-thiol acetic ester (THEIC-TEA) or tris(2-hydroxy ethyl)isocyanurate tri-thiol propionic ester (THEIC-TPA), and these tri-thiol compounds all can obtain by the esterification between corresponding trihydroxy-compound and Thiovanic acid or the thiohydracrylic acid;
Described diolefin compound CD is
R wherein
1Be ethyl or propyl group, CD can obtain by Hydroxyethyl acrylate or Propylene glycol monoacrylate and methacrylic chloride reaction;
(b) D3 obtains first-generation end sulfydryl hyperbranched polymer NP1-HSH with two sulfydryl secondary amine compound BA2 at 20-80 ℃ of stirring reaction 5-10h;
Described compd B A
2Structural formula be
R wherein
2Be ethyl or sec.-propyl;
Compd B A2 can be by thiirane or methyl thiirane and ammoniacal liquor reaction acquisition;
(c) first-generation end sulfydryl hyperbranched polymer NP1-HSH and glycidyl methacrylate (GMA) stir a 2-5h at-10-20 ℃ and carry out mercaptan-alkene hydrocarbon click-reaction, obtain first-generation sulfur-bearing hyperbranched epoxy resin (NP1-HEP), are called for short G1.
Utilize first-generation end sulfydryl hyperbranched polymer NP1-HSH to continue to react and can prepare second, third generation, the 4th generation sulfur-bearing hyperbranched epoxy resin (being respectively NP2-HEP, NP3-HEP, NP4-HEP) (being called for short respectively G2, G3, G4) by (a) and (b), (c) step successively, prepared four generation the sulfur-bearing hyperbranched epoxy resin the about 2000-30000g/mol of molecular weight.
When preparing described first-generation sulfur-bearing hyperbranched epoxy resin (NP1-HEP), the mol ratio of A3, CD, BA2, GMA is 1:3.05-3.20:3.10-3.30:6.10-6.30;
When preparing described s-generation sulfur-bearing hyperbranched epoxy resin (NP2-HEP), the mol ratio of NP1-HSH, CD, BA2, GMA is 1:6.10-6.50:6.20-6.30:12.50-13.00;
When preparing described third generation sulfur-bearing hyperbranched epoxy resin (NP3-HEP), the mol ratio of NP2-HSH, CD, BA2, GMA is 1:12.50-13.10:12.60-13.50:25.10-26.20;
When preparing described the 4th generation sulfur-bearing hyperbranched epoxy resin (NP4-HEP), the mol ratio of NP3-HSH, CD, BA2, GMA is 1:25.10-26.50:26.00-27.20:50.60-53.00.
This preparation method's more concrete step is as follows:
(a) with tri-thiol compound A-13 and diolefin compound CD at-10-20 ℃ stirring reaction 2-5h, then the hydroquinone of polymerization retarder that adds the 0.5-1.0% of Compound C D quality, then be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive CD, obtain the acrylate monomer D3 of polyfunctionality;
(b) D3 and two sulfydryl secondary amine compound BA2 are under the condition of 2mmHg 120 ℃ of vacuum tightnesss behind 20-80 ℃ of stirring reaction 5-10h, remove excessive BA2, obtain first-generation end sulfydryl hyperbranched polymer NP1-HSH;
(c) first-generation end sulfydryl hyperbranched polymer NP1-HSH and glycidyl methacrylate (GMA) are at-10-20 ℃ stirring reaction 2-5h, then the hydroquinone of polymerization retarder that adds the 0.5-1.0% of GMA quality, then be under the condition of 2mmHg 140 ℃ of vacuum tightnesss, remove excessive GMA, obtain first-generation sulfur-bearing hyperbranched epoxy resin (NP1-HEP), i.e. G1.
First-generation end sulfydryl hyperbranched polymer NP1-HSH prepares s-generation sulfur-bearing hyperbranched epoxy resin NP2-HEP, i.e. G2 by (a) and (b), the reaction of (c) step again;
S-generation end sulfydryl hyperbranched polymer NP2-HSH prepares third generation sulfur-bearing hyperbranched epoxy resin NP3-HEP, i.e. G3 by (a) and (b), the reaction of (c) step again;
Third generation end sulfydryl hyperbranched polymer NP3-HSH prepares the 4th generation sulfur-bearing hyperbranched epoxy resin NP2-HEP, i.e. G4 by (a) and (b), the reaction of (c) step again.
The prepared sulfur-bearing hyperbranched epoxy resin of the present invention has lower viscosity and higher thermotolerance, is expected to be applied to the fields such as the enhancing of high-temperature resistance adhesive, high-temperature resistant coating, the low volatilization of environmental protection coating, low volatilization resin, Resins, epoxy is toughness reinforcing.
Technical scheme of the present invention compared with prior art has following advantage and beneficial effect:
1, the present invention is incorporated into element sulphur in the structure of sulfur-bearing hyperbranched epoxy resin, can promote the curing of Resins, epoxy, reduces solidification value;
2, the mercaptan-alkene hydrocarbon click-reaction technology that adopts of the present invention has that temperature of reaction is low, the efficient high, and the reaction times is short, is a kind of energy-saving technique of new preparation Resins, epoxy;
3, technical scheme of the present invention need not the techniques such as organic solvent and washing in preparation sulfur-bearing hyperbranched epoxy resin process, has avoided conventional organic solvents and washing preparation Resins, epoxy to the pollution of environment;
4, the preparation technology of sulfur-bearing hyperbranched epoxy resin of the present invention is simple, and raw materials cost is low, is suitable for suitability for industrialized production.
5, sulfur-bearing hyperbranched epoxy resin of the present invention has the enhancing toughening functions to ordinary epoxy resin, is expected to be widely used in the toughness reinforcing field of enhancing of Resins, epoxy;
6, sulfur-bearing hyperbranched epoxy resin viscosity of the present invention low, add in the bisphenol A type epoxy resin and can significantly lower its viscosity, play the effect of reactive thinner, be expected to be applied to solvent-free, low volatilization epoxypaint field.
Embodiment
The present invention will be described in detail below in conjunction with specific embodiment, but the protection domain that these embodiment do not limit the present invention in any way.
That the molecular weight determination of product adopts is the GPC of Britain PL company, and oxirane value adopts the hydrochloric acid acetone method of national standard to measure, and viscosity adopts the Brookfield viscometer to measure under 25 ℃ of conditions.
Below compound A-13 and Compound C D among all embodiment be present inventor's self-control, concrete preparation process is as follows:
The preparation of compound A-13:
Obtain by corresponding trivalent alcohol and Thiovanic acid or thiohydracrylic acid esterification reaction, with the example that is prepared as of trimethylolpropane tris mercaptoacetate (TMP-TEA) its preparation process is described.0.1mol TriMethylolPropane(TMP), 0.45mol thiohydracrylic acid, 1.6g tosic acid add in the four-hole boiling flask with prolong, thermometer, water trap and agitator, slowly are warming up to 160 ℃, stirring reaction is about 6 hours, stopped reaction.The saturated aqueous solution 20g that adds sodium bicarbonate, then pour layering in the separating funnel into, be washed till the pH value with 20ml distilled water is 6-7 at every turn, is that rotary evaporation is removed impurity under the 2-3mmHg condition with oil reservoir 120 ℃ of left and right sides vacuum tightnesss then, obtain light yellow transparent liquid 33.8g, productive rate is about 95%.All the other A3 compounds can obtain with similar method, and productive rate is between 92-96%.
The preparation of Compound C D:
0.2mol methacrylic chloride and 0.2g Resorcinol are added in the four-hole boiling flask with HCl recovery device, thermometer, constant pressure funnel and agitator, 0.15mol Hydroxyethyl acrylate or Propylene glycol monoacrylate are joined constant pressure funnel.Slowly drip at ambient temperature Hydroxyethyl acrylate or Propylene glycol monoacrylate, after dropwising, slowly be warming up to about 60 ℃, continued stirring reaction 4-5 hour.Add 10ml distilled water, then layering in the separating funnel, be washed till the pH value with 10ml distilled water is 6-7 at every turn, is that rotary evaporation is removed impurity under the 2-3mmHg condition with oil reservoir 60 ℃ of left and right sides vacuum tightnesss then, obtain colourless extremely light yellow transparent liquid, productive rate is about 85%.
Embodiment 1
With 0.1mol trimethylolpropane tris mercaptoacetate (TMP-TEA) and 0.305mol Hydroxyethyl acrylate-methacrylic ester (MA-EA-MMA) at-5-0 ℃ stirring reaction 5h, then 0.5% the Resorcinol that adds the MA-EA-MMA quality, then be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive MA-EA-MMA, obtain to contain the acrylate monomer (D3-A) of the two keys of 3mol; Then adding 0.31mol 3-mercaptoethanol amine behind 20 ℃ of stirring reaction 10h, is under the condition of 2mmHg 120 ℃ of vacuum tightnesss, removes excessive 3-mercaptoethanol amine, obtains first-generation end sulfydryl hyperbranched polymer NP1-HSH-A; Then add the 0.61mol glycidyl methacrylate, behind-5-0 ℃ stirring reaction 5h, 0.5% the Resorcinol that adds the glycidyl methacrylate quality, then be under the condition of 2mmHg 140 ℃ of vacuum tightnesss, remove excessive glycidyl methacrylate, obtain first-generation sulfur-bearing hyperbranched epoxy resin (G1-A) weak yellow liquid, testing its number-average molecular weight is 2100g/mol, 25 ℃ of lower viscosity are 400cp, and oxirane value is 0.28mol/100g.
Embodiment 2
With 0.1mol trimethylolpropane tris mercaptopropionic acid ester (TMP-TPA) and 0.32mol Propylene glycol monoacrylate-methacrylic ester (MA-PA-MMA) at-5-0 ℃ stirring reaction 4h, then 1.0% the Resorcinol that adds the MA-PA-MMA quality, then be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive MA-PA-MMA, obtain to contain the acrylate monomer (D3-B) of the two keys of 3mol; Then adding 0.32mol dimercapto α-amino isopropyl alcohol behind 40 ℃ of stirring reaction 8h, is under the condition of 2mmHg 120 ℃ of vacuum tightnesss, removes excessive dimercapto α-amino isopropyl alcohol, obtains first-generation end sulfydryl hyperbranched polymer NP1-HSH-B; Then add the 0.62mol glycidyl methacrylate, behind-5-0 ℃ stirring reaction 4h, 1.0% the Resorcinol that adds the GMA quality, then be under the condition of 2mmHg 140 ℃ of vacuum tightnesss, remove excessive GMA, obtain first-generation sulfur-bearing hyperbranched epoxy resin (G1-B) weak yellow liquid, testing its number-average molecular weight is 2300g/mol, viscosity is 600cp in the time of 25 ℃, and oxirane value is 0.26mol/100g.
Embodiment 3
With 0.1mol tris(2-hydroxy ethyl)isocyanurate tri-thiol propionic ester (THEIC-TPA) and 0.31mol Propylene glycol monoacrylate-methacrylic ester (MA-PA-MMA) at 0-5 ℃ of stirring reaction 4h, then 1.0% the Resorcinol that adds the MA-PA-MMA quality, then be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive MA-PA-MMA, obtain to contain the acrylate monomer (D3-C) of the two keys of 3mol; Then adding 0.32mol dimercapto α-amino isopropyl alcohol behind 60 ℃ of stirring reaction 6h, is under the condition of 2mmHg 120 ℃ of vacuum tightnesss, removes excessive dimercapto α-amino isopropyl alcohol, obtains first-generation end sulfydryl hyperbranched polymer NP1-HSH-C; Then add the 0.62mol glycidyl methacrylate, behind 0-5 ℃ of stirring reaction 4h, 1.0% the Resorcinol that adds the GMA quality, then be under the condition of 2mmHg 140 ℃ of vacuum tightnesss, remove excessive GMA, obtain first-generation sulfur-bearing hyperbranched epoxy resin (G1-C) weak yellow liquid, testing its number-average molecular weight is 2500g/mol, viscosity is 700cp in the time of 25 ℃, and oxirane value is 0.25mol/100g.
Embodiment 4
With 0.1mol tris(2-hydroxy ethyl)isocyanurate tri-thiol acetic ester (THEIC-TEA) and 0.15mol Propylene glycol monoacrylate-methacrylic ester (MA-PA-MMA) and 0.16mol Hydroxyethyl acrylate-methacrylic ester (MA-EA-MMA) at 5-10 ℃ of stirring reaction 3h, then 1.0% the Resorcinol that adds the total mass of MA-PA-MMA and MA-EA-MMA, be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive MA-PA-MMA and/or MA-EA-MMA, obtain to contain the acrylate monomer (D3-D) of the two keys of 3mol; Then adding 0.32mol dimercapto α-amino isopropyl alcohol behind 80 ℃ of stirring reaction 5h, is under the condition of 2mmHg 120 ℃ of vacuum tightnesss, removes excessive dimercapto α-amino isopropyl alcohol, obtains first-generation end sulfydryl hyperbranched polymer (NP1-HSH-D); Then add the 0.62mol glycidyl methacrylate, behind 10-20 ℃ of stirring reaction 2h, 1.0% the Resorcinol that adds the GMA quality, then be under the condition of 2mmHg 140 ℃ of vacuum tightnesss, remove excessive GMA, obtain first-generation sulfur-bearing hyperbranched epoxy resin (G1-D) weak yellow liquid, testing its number-average molecular weight is 2400g/mol, viscosity is 650cp in the time of 25 ℃, and oxirane value is 0.26mol/100g.
Embodiment 5
With 0.03mol THEIC-TPA, 0.02mol THEIC-TEA, 0.05mol TMP-TPA, 0.11mol Propylene glycol monoacrylate-methacrylic ester (MA-PA-MMA) and 0.21mol Hydroxyethyl acrylate-methacrylic ester (MA-EA-MMA) at 15-20 ℃ of stirring reaction 2h, then 1.0% the Resorcinol that adds MA-EA-MMA and MA-PA-MMA total mass, be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive MA-PA-MMA and/or MA-EA-MMA, obtain to contain the acrylate monomer (D3-E) of the two keys of 3mol; Then add 0.15mol dimercapto α-amino isopropyl alcohol and 0.18mol 3-mercaptoethanol amine behind 80 ℃ of stirring reaction 5h, be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive dimercapto α-amino isopropyl alcohol and/or 3-mercaptoethanol amine, obtain first-generation end sulfydryl hyperbranched polymer (NP1-HSH-E); Then add the 0.63mol glycidyl methacrylate, behind 10-15 ℃ of stirring reaction 3h, 1.0% the Resorcinol that adds the GMA quality, then be under the condition of 2mmHg 140 ℃ of vacuum tightnesss, remove excessive GMA, obtain first-generation sulfur-bearing hyperbranched epoxy resin (G1-E) weak yellow liquid, testing its number-average molecular weight is 2350g/mol, viscosity is 600cp in the time of 25 ℃, and oxirane value is 0.26mol/100g.
Embodiment 6
With first-generation end sulfydryl hyperbranched polymer (NP1-HSH-A) 0.1mol of embodiment 1 preparation and 0.63mol Hydroxyethyl acrylate-methacrylic ester (MA-EA-MMA) at 0-5 ℃ of stirring reaction 4h, then 1.0% the Resorcinol that adds the MA-EA-MMA quality, be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive MA-EA-MMA; Then adding 0.62mol 3-mercaptoethanol amine behind 60 ℃ of stirring reaction 8h, is under the condition of 2mmHg 120 ℃ of vacuum tightnesss, removes excessive 3-mercaptoethanol amine, obtains s-generation end sulfydryl hyperbranched polymer (NP2-HSH-A).Then add the 1.26mol glycidyl methacrylate, behind 5-10 ℃ of stirring reaction 5h, 0.5% the Resorcinol that adds the GMA quality, be under the condition of 2mmHg 140 ℃ of vacuum tightnesss, remove excessive GMA, obtain s-generation sulfur-bearing hyperbranched epoxy resin (G2-A) weak yellow liquid, testing its number-average molecular weight is 4900g/mol, viscosity is 800cp in the time of 25 ℃, and oxirane value is 0.26mol/100g.
Embodiment 7
With s-generation end sulfydryl hyperbranched polymer (NP2-HSH-A) 0.1mol of embodiment 6 preparation and 1.30mol Propylene glycol monoacrylate-methacrylic ester (MA-PA-MMA) at 5-10 ℃ of stirring reaction 4h, then 1.0% the Resorcinol that adds the MA-PA-MMA quality, be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive MA-PA-MMA.Then adding 1.30mol dimercapto α-amino isopropyl alcohol behind 80 ℃ of stirring reaction 8h, is under the condition of 2mmHg 120 ℃ of vacuum tightnesss, removes excessive dimercapto α-amino isopropyl alcohol, obtains third generation end sulfydryl hyperbranched polymer (NP3-HSH-A).Then add the 2.60mol glycidyl methacrylate, behind 10-15 ℃ of stirring reaction 5h, 0.5% the Resorcinol that adds the GMA quality, be under the condition of 2mmHg 140 ℃ of vacuum tightnesss, remove excessive GMA, obtain third generation sulfur-bearing hyperbranched epoxy resin (G3-A) weak yellow liquid, testing its number-average molecular weight is 11500g/mol, viscosity is 1200cp in the time of 25 ℃, and oxirane value is 0.23mol/100g.
Embodiment 8
With third generation end sulfydryl hyperbranched polymer (NP3-HSH-A) 0.01mol of embodiment 7 preparation and 0.26mol Propylene glycol monoacrylate-methacrylic ester (MA-PA-MMA) at 15-20 ℃ of stirring reaction 3h, then 1.0% the Resorcinol that adds the MA-PA-MMA quality, be under the condition of 2mmHg 120 ℃ of vacuum tightnesss, remove excessive MA-PA-MMA.Then adding 0.27mol dimercapto α-amino isopropyl alcohol behind 60 ℃ of stirring reaction 10h, is under the condition of 2mmHg 120 ℃ of vacuum tightnesss, removes excessive dimercapto α-amino isopropyl alcohol, obtains the 4th generation end sulfydryl hyperbranched polymer (NP4-HSH-A).Then add the 0.52mol glycidyl methacrylate, behind 15-20 ℃ of stirring reaction 5h, 0.5% the Resorcinol that adds the GMA quality, be under the condition of 2mmHg 140 ℃ of vacuum tightnesss, remove excessive GMA, obtain the 4th generation sulfur-bearing hyperbranched epoxy resin (G4-A) weak yellow liquid, testing its number-average molecular weight is 22500g/mol, viscosity is 2100cp in the time of 25 ℃, and oxirane value is 0.23mol/100g.
Sulfur-bearing hyperbranched epoxy resin 9wt%/bisphenol A type epoxy resin (E51 that the embodiment 1～8 of this embodiment part is obtained, oxirane value 0.51mol/100g, viscosity at ambient temperature is 15600cp, commercially available) 91wt%, solidifying agent (DETA-AN) is for waiting affixture mixing (consumption of solidifying agent is as the criterion with the stoichiometry of amino and epoxy group(ing) complete reaction) of mole diethylenetriamine and vinyl cyanide, mixture is cast in the mould, self-vulcanizing 4 hours, solidified again 2 hours after being warming up to about 80 ℃, take out the rear demoulding of sample cooling, room temperature is placed the performance of difference test material after 12 hours, and the result is as shown in table 1.Wherein, the tensile strength of material is tested according to ASTM D638-82a, the bending property of material is tested according to ASTM D790M-92 standard, the shock strength of material is tested according to ASTM D256-81 standard, the fracture toughness property of material is tested according to ASTM D5045-91a standard, the thermal characteristics of material (second-order transition temperature) is tested by DSC according to ASTM3418-82, and the temperature rise rate of test is 10 ℃/min.
Table 1 is the performance behind the prepared sulfur-bearing hyperbranched epoxy resin of embodiment 1-8 modified bisphenol A type Resins, epoxy respectively
Claims (10)
1. sulfur-bearing hyperbranched epoxy resin, its structural formula is Gn,
In the formula, A, B, C, D represent respectively-SH ,-NH-, CH
2=C (CH
3) COO-and CH
2=CHCOO-;
In the formula, compound GMA is glycidyl methacrylate;
Wherein compound A-13 is trimethylolpropane tris mercaptoacetate, trimethylolpropane tris mercaptopropionic acid ester, tris(2-hydroxy ethyl)isocyanurate tri-thiol acetic ester or tris(2-hydroxy ethyl)isocyanurate tri-thiol propionic ester.
2. a kind of sulfur-bearing hyperbranched epoxy resin according to claim 1, its structural formula is
3. a kind of sulfur-bearing hyperbranched epoxy resin according to claim 1, its structural formula is
4. a kind of sulfur-bearing hyperbranched epoxy resin according to claim 1, its structural formula is
5. a kind of sulfur-bearing hyperbranched epoxy resin according to claim 1, its structural formula is
6. the preparation method of a sulfur-bearing hyperbranched epoxy resin claimed in claim 1, its step is as follows:
(a) tri-thiol compound A-13 and diolefin compound CD are prepared the acrylate monomer D3 of polyfunctionality at-10-20 ℃ stirring reaction 2-5h;
Described tri-thiol compound A-13 is trimethylolpropane tris mercaptoacetate, trimethylolpropane tris mercaptopropionic acid ester, tris(2-hydroxy ethyl)isocyanurate tri-thiol acetic ester or tris(2-hydroxy ethyl)isocyanurate tri-thiol propionic ester;
Described diolefin compound CD is
R wherein
1Be ethyl or propyl group;
(b) D3 obtains first-generation end sulfydryl hyperbranched polymer NP1-HSH with two sulfydryl secondary amine compound BA2 at 20-80 ℃ of stirring reaction 5-10h;
Described compd B A
2Structural formula be
R wherein
2Be ethyl or sec.-propyl;
(c) first-generation end sulfydryl hyperbranched polymer NP1-HSH and glycidyl methacrylate GMA stir a 2-5h at-10-20 ℃ and carry out mercaptan-alkene hydrocarbon click-reaction, obtain first-generation sulfur-bearing hyperbranched epoxy resin G1;
Utilize first-generation end sulfydryl hyperbranched polymer NP1-HSH to continue to prepare second, third generation, the 4th generation sulfur-bearing hyperbranched epoxy resin G2, G3, G4 by (a) and (b), the reaction of (c) step successively.
7. preparation method according to claim 6, it is characterized in that: when preparing described first-generation sulfur-bearing hyperbranched epoxy resin, the mol ratio of A3, CD, BA2, GMA is 1:3.05-3.20:3.10-3.30:6.10-6.30.
8. preparation method according to claim 6, it is characterized in that: when preparing described s-generation sulfur-bearing hyperbranched epoxy resin, the mol ratio of first-generation end sulfydryl hyperbranched polymer NP1-HSH, CD, BA2, GMA is 1:6.10-6.50:6.20-6.30:12.50-13.00.
9. preparation method according to claim 6, it is characterized in that: when preparing described third generation sulfur-bearing hyperbranched epoxy resin, the mol ratio of s-generation end sulfydryl hyperbranched polymer NP2-HSH, CD, BA2, GMA is 1:12.50-13.10:12.60-13.50:25.10-26.20.
10. preparation method according to claim 6, it is characterized in that: prepare described the 4th generation during the sulfur-bearing hyperbranched epoxy resin, the mol ratio of third generation end sulfydryl hyperbranched polymer NP3-HSH, CD, BA2, GMA is 1:25.10-26.50:26.00-27.20:50.60-53.00.
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Cited By (11)
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| CN105315481A (en) * | 2015-11-30 | 2016-02-10 | 赤峰富龙市政公用工程有限责任公司 | Method for preparing flame-retardant phenolic resin low temperature foam material |
| CN105732859A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Polymers containing sulfur terminal and preparing method thereof |
| CN106832219A (en) * | 2017-01-22 | 2017-06-13 | 中南民族大学 | A kind of flame-retardant hyperbranched epoxy resin of phosphorus-nitrogen-containing halogen-free and preparation method thereof |
| CN106866643A (en) * | 2016-10-26 | 2017-06-20 | 纪克兵 | A kind of preparation method and applications containing sulfur crosslinking agent |
| CN107459644A (en) * | 2017-09-13 | 2017-12-12 | 朱远哲 | A kind of dissaving polymer and the method that the polymer is prepared based on otherness epoxy ring opening reaction |
| CN108794726A (en) * | 2018-04-26 | 2018-11-13 | 中南民族大学 | A kind of degradable hyperbranched epoxy resin of sulfur-bearing and preparation method thereof |
| CN109021229A (en) * | 2018-08-06 | 2018-12-18 | 武汉大学 | A kind of preparation method and applications of sulfur-bearing hyperbranched polyglycidyl ether copolymer |
| CN109913082A (en) * | 2017-12-13 | 2019-06-21 | 武汉赫斯特涂层材料股份有限公司 | A kind of organic-silicon-modified sulfur-bearing epoxy heavy-duty anticorrosive coating and preparation method thereof |
| US10457865B2 (en) | 2016-06-14 | 2019-10-29 | Shenzhen China Star Optoelectronics Technology Co., Ltd | Water-soluble quantum dot (QD) and manufacturing methods of the water-soluble QD and the QD films |
| US11098166B2 (en) | 2018-04-26 | 2021-08-24 | South central university for nationalities | Degradable hyperbranched epoxy resin and preparation method thereof |
| CN113527637A (en) * | 2021-08-09 | 2021-10-22 | 哈尔滨工业大学 | Preparation and degradation method of thermosetting epoxy resin capable of being degraded by gamma ray irradiation |
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| CN105732859A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Polymers containing sulfur terminal and preparing method thereof |
| CN105732859B (en) * | 2014-12-10 | 2018-06-01 | 中国石油天然气股份有限公司 | A kind of polymer of sulfur-bearing end and preparation method thereof |
| CN105315481B (en) * | 2015-11-30 | 2018-08-14 | 赤峰富龙市政公用工程有限责任公司 | A method of preparing flame retardant type phenolic resin low temp expanded material |
| CN105315481A (en) * | 2015-11-30 | 2016-02-10 | 赤峰富龙市政公用工程有限责任公司 | Method for preparing flame-retardant phenolic resin low temperature foam material |
| US10457865B2 (en) | 2016-06-14 | 2019-10-29 | Shenzhen China Star Optoelectronics Technology Co., Ltd | Water-soluble quantum dot (QD) and manufacturing methods of the water-soluble QD and the QD films |
| CN106866643A (en) * | 2016-10-26 | 2017-06-20 | 纪克兵 | A kind of preparation method and applications containing sulfur crosslinking agent |
| CN106832219A (en) * | 2017-01-22 | 2017-06-13 | 中南民族大学 | A kind of flame-retardant hyperbranched epoxy resin of phosphorus-nitrogen-containing halogen-free and preparation method thereof |
| CN106832219B (en) * | 2017-01-22 | 2019-01-29 | 中南民族大学 | A kind of containing phosphorus-nitrogen halogen-free flame-retardant hyperbranched epoxy resin and preparation method thereof |
| CN107459644A (en) * | 2017-09-13 | 2017-12-12 | 朱远哲 | A kind of dissaving polymer and the method that the polymer is prepared based on otherness epoxy ring opening reaction |
| CN109913082B (en) * | 2017-12-13 | 2020-11-06 | 武汉赫斯特涂层材料股份有限公司 | Organic silicon modified sulfur-containing epoxy heavy-duty anticorrosive paint and preparation method thereof |
| CN109913082A (en) * | 2017-12-13 | 2019-06-21 | 武汉赫斯特涂层材料股份有限公司 | A kind of organic-silicon-modified sulfur-bearing epoxy heavy-duty anticorrosive coating and preparation method thereof |
| WO2019206200A1 (en) * | 2018-04-26 | 2019-10-31 | 中南民族大学 | Sulphur-containing degradable hyperbranched epoxy resin and preparation method therefor |
| US10808071B2 (en) | 2018-04-26 | 2020-10-20 | South central university for nationalities | Degradable sulfur-containing hyperbranched epoxy resin and preparation method thereof |
| CN108794726A (en) * | 2018-04-26 | 2018-11-13 | 中南民族大学 | A kind of degradable hyperbranched epoxy resin of sulfur-bearing and preparation method thereof |
| US11098166B2 (en) | 2018-04-26 | 2021-08-24 | South central university for nationalities | Degradable hyperbranched epoxy resin and preparation method thereof |
| CN109021229A (en) * | 2018-08-06 | 2018-12-18 | 武汉大学 | A kind of preparation method and applications of sulfur-bearing hyperbranched polyglycidyl ether copolymer |
| CN113527637A (en) * | 2021-08-09 | 2021-10-22 | 哈尔滨工业大学 | Preparation and degradation method of thermosetting epoxy resin capable of being degraded by gamma ray irradiation |
| CN113527637B (en) * | 2021-08-09 | 2022-05-03 | 哈尔滨工业大学 | Preparation and degradation method of thermosetting epoxy resin capable of being degraded by gamma ray irradiation |
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